Water blocking gel composition

ABSTRACT

A water blocking composition for sheathed stranded cables consisting essentially of a gel of (a) a major proportion by weight of a substantially non-volatile petroleum based oil, said oil being an aromatic extract containing aromatic and saturated hydrocarbons and sulfur containing polar compounds in which has been dispersed (b) a minor proportion by weight of a solid gellant which is insoluble in said oil and which does not melt below 100*C., said gellant being selected from the group consisting of a bentonite clay based gellant and a sub-micron particle sized silica gellant, the gel being substantially devoid of any gellant which is soluble in the oil and melts below 100*C.

United States atent 1191 Foord et a1. Sept. 2, 1975 [54] WATER BLOCKING GEL COMPOSITION 2.681.314 6/1954 Skinner ct al 252/317 x 3.733.426 5/1973 Kaufman ct a1. 174/116 x [75] Inventors Stanley Gmrge Fwrd, Harlow; 3,775,548 11 1973 Zinser,.1r., et al 174/116 x Walter Eric Simpson, Ware; Peter Ivan Aitken Martin, Bishops Stortford, all of England Assignee: International Standard Electric Corporation, New York, N.Y.

Filed: Oct. 19, 1972 Appl. No.: 298,811

US. Cl 252/317; 161/172; 174/23 C; 174/24; 174/105 R; 174/110 R; 174/116; 252/635; 252/314 Int. Cl BOlj 13/00; HOlb 3/O2iHO1b 3/22 Field of Search 252/317, 63.5; 174/105 R, 174/110 R, 116, 23 C, 24

156] References Cited UNITED STATES PATENTS 2,531,440 11/1950 Jordan 252/635 X Primary Examiner-Richard D. Lovering Attorney, Agent, or FirmJ. B. Raden; H. J. Holt [57] ABSTRACT A water blocking composition for sheathed stranded cables consisting essentially of a gel of (a) a major proportion by weight of a substantially non-volatile petroleum based oil, said oil being an aromatic extract containing aromatic and saturated hydrocarbons and sulfur containing polar compounds in which has been dispersed (b) a minor proportion by weight of a solid gellant which is insoluble in said oil and which does not melt below 100C., said gellant being selected from the group consisting of a bentonite clay based gellant and a sub-micron particle sized silica gellant, the gel being substantially devoid of any gellant which is soluble in the oil and melts below 100C.

3 Claims, 4 Drawing Figures App/ed Piessure aa/I Pi-WEWEIFSEF 21975 3,903,013

sum 1. OF 2 F/ow F/ow 9 0 2 Stress WATER BLOCKING GEL COMPOSITION This invention relates to water-blocking compounds for sheathed stranded cables.

According to the present invention there is provided a water blocking compound for sheathed stranded cables, the compound being a gel consisting of a major proportion by weight of a substantially non-volatile liquid in which has been dispersed a minor proportion by weight of a solid gellant which is insoluble in said liquid and which does not melt below 100C, the gell being substantially devoid of any gellant which is soluble in the liquid and/or melts below l()OC.

The invention also resides in a sheathed stranded cable incorporating a water blocking compound of the type defined in the preceding paragraph.

There follows a description of water blocking compounds embodying the invention in preferred forms. For the purposes of comparison reference is also made to the properties of petrolatum which previously has been used as a water blocking compound for sheathed stranded cables. The description refers to the accompanying drawings in which:

FIG. 1 depicts the flow curves characteristic of a hypothetical ideal filling compound,

FIG. 2 depicts the flow curves of petrolatum and viscous oils at various temperatures, and

FIGS. 3 and 4 depict flow curves at respectively 22C and 70C of a set of gels formulated from different grades of aromatic extract in which an activated modified clay has been dispersed.

As a basis for specifying the required material properties of a water blocking compound it is helpful to consider two specific features relating respectively to manufacture andfinal properties of the cable. ln manufacture it is possible to pre-coat the individual wires or insulated conductors with filling compound prior to the stranding operation, but it is preferred to pump the compound into the dies of the stranding machine as each layer is formed, to ensure complete filling of the cable. Whatever procedure is adopted the flow properties of the compound should be such as to enable a reasonable flow rate to be achieved with a convenient value of pumping pressure. At the same time the compound, as it appears in the finished cable, should not flow when subjected to a specified gradient of hydrostatic pressure. In other words the material should show a measure of plasticity providing a yield stress exceeding a certain specified value. As a minimum this gradient must exceed that set by the weight of compound in a vertically held open-ended length of cable, in order to prevent drainage from the cable. Gradients of this order are commonly quoted in test specifications for filled plastic insulated telephone subscriber cables.

These two criteria for the consistency of a filling compound are fundamental, and must apply for all conditions of exposure, in particular at all temperatures encountered during manufacture and subsequent service of the cable. They are exemplified by the relationships, shown in FIG. 1, between flow and shear stress of a hypothetical compound. In this Figure:

8,, is the stress below which drainage or movement of the compound must not occur, and

S is the stress at which compound begins to flow.

Curves 1-3 are idealised characteristics of a suitable compound, at three temperatures. Curves I and 3 are for the minimum and maximum service temperatures of the cable; curve 2 is for ambient temperature during manufacture. Curve 4 is the flow curve of the material at the lowest temperature at which it can conveniently be pumped. Below this temperature the apparent viscosity, the ratio of applied shearing stress to rate of shear, becomes too large to achieve adequate flow rates atsuitable pumping pressures.

it will be noted that:

a. Drainage or longitudinal flow of compound in the cable does not occur, over the whole service temperature range b. The compound can be pumped without preheating c. At the bottom service temperature flow will occur at a sufficiently moderate stress to permit flexing of the cable without damage to its constituent parts even though the compound may have too high an apparent viscosity for pumping.

These requirements have all been concerned with rheological properties. Certain additional requirements need to be met by an ideal filling compound. The compound must be immiscible with water, and should possess the following features:

d. Thermal expansion coefficient over the cable service temperature range should be as low as possible, to prevent formation of voids during cooling. Such voids provide a seepage path for water, particularly between stranded conductors and an outer sheath.

e. The compound must not attack insulating and sheathing materials to an extent which will significantly detract from their performance.

f. On standing, the compound must not divide into separate phases, if any one of these separated phases will not meet the performance requirements of the original compound.

g. In the case of telecommunication or power cables the electrical conductivity must be low.

h. The compound must be free from toxic hazards, and

have handling properties acceptable to manufacturing and installation operating personnel; thus it should not be too tacky.

i. The compound must have an acceptably low vapour pressure so that over a reasonable period of service in a cable its properties do not significantly deteriorate from evaporation through vapour permeable cable sheathing.

Petrolatum, a mixture of microcrystalline petroleum wax and oil, has been widely used, since it shows plastic behaviour, i.e. it exhibits a non zero yield stress beneath which there is no flow, as shown by curves 5-7 in FIG. 2, which are flow curves characteristic for low, medium and high temperatures respectively. The plasticity is induced by the microcrystalline wax. However the wax melts or dissolves in the oil as the temperature is increased, resulting in a lower yield stress and a tendency to drain at high temperatures (curve 7). On cooling, some wax separates, giving at first the satisfactory characteristic of curve 6, but further cooling results in further increase in the yield stress and the characteristic is given by the curve 5. At this stage the apparent viscosity at normal pumping pressures is too large to give an adequate flow rate. This stage is commonly reached above normal factory temperatures, and it becomes necessary to heat the compound to pump it, an

undesirable and expensive expedient. Still further cooling below factory ambient may raise the yield stress so much that flexibility of the cable is impaired.

Compositional variations on the basic mixture enable the service range to be raised or lowered, but not appreciably extended. For example, petroleum waxes alone have been proposed, but have to be pumped hot and have insufficient flexibility at low temperature. A further disadvantage of compositions containing petroleum wax is the large decrease in volume when the wax solidifies or comes out of solution on cooling. A 10 percent shrinkage has been observed on cooling a commercial petrolatum filling compound from 80C to room temperature.

Water blocking gels compounded in accordance with the present invention may include in addition to the nonvolatile liquid and solid gellant minor proportions of other ingredients such as anti-oxidants, stabilisers, colour base, and dispersing agents. In particular, where the liquid is non-polar, as will generally be the case for telecommunications cables, the use of certain types of gellant will require the admixture of a small quantity of polar additive in order for the gellant to function effectively with the nonpolar type of dispersant.

A wide range of liquids can be used as the major constituent, depending upon the type of cable in which it is to be used. For a particular application the choice is narrowed by the need to meet additional requirements. Cables for electrical purposes for instance will typically be required to operate in a temperature range within the limits of 30C to +lC. The liquid should not significantly attack insulating and sheathing materials, in particular polyethylene and polypropylene, and should have low electrical conductivity. For such purposes we have found that hydrocarbon-based liquids derived from petroleum may be used, such as the class of materials known in the industry as Aromatic Ex tracts, or Process Oils. These are relatively low cost materials whose principal uses are as extenders, plasticisers and general processing aids for rubber and plastic compositions. Typically they comprise 75-85 percent by weight aromatic hydrocarbons, -l5 percent saturated hydrocarbons, and sulphur containing polar compounds making up the balance. The hydrocarbons have molecular weights generally within the range of 300-600, and are practically non-volatile at 100C. However oils containing a lower proportion of aromat ics and a greater proportion of saturated hydrocarbons may be used.

A number of solid materials are known which act as gellants when mixed with liquids in which they do not dissolve, for example granulated mica, ultrafine silica, and certain natural clays. These vary in efficiency depending upon the nature of the liquid with which they are compounded and the ability to activiate the interface between solid and liquid. We have found that a group of specially processed clays sold under the Registered Trade Marks BENTONE or BARAGEL are particularly effective when used in conjunction with bydrocarbon oils of the type described above. These materials are a class of product resulting from cation exchange reactions between organic bases and certain clay minerals and are supplied as fine powders, the particles of which have the form of platelets with a high ratio of diameter to thickness. The organic constituent in the surface of the particles is solvated by various liquids. in the case of non-polar liquids such as hydrocarbon oils solvation is assisted by the addition of small amounts of polar liquids such as alcohols, ketones, cs-

ters, etc.

For the preparation of such compositions the major liquid constituent is first premixed with the solid gellant in any conventional type of medium speed mixer. Further additives are incorporated either with the liquid or the solid or added to the premix. The premix is then passed through a mill such as a colloid mill in which it is subjected to high shearing forces which thoroughly delaminate and disperse the gellant and produce a stable gel. Typically the amount of gellant lies in the range 0.5 to 10 percent by weight of the total composition.

Before giving examples of compositions, a brief description will be given of the method used for testing the flow properties, and their relationship to perfor mance during manufacture and service of filled cables. The flow requirements have been indicated qualitatively in FIG. 1, which shows flow as a function of shear stress. Quantitative results have been obtained by the use of an extrusion rheometer in which fluid pressure is applied to the compound in a cylinder causing it to flow out through a small orifice, the rate of extrusion being determined as a function of applied pressure (which is related to the stress). The orifice diameter was chosen to be comparable withthat of the interstices in a typical stranded cable, and the orifice length to be ten times the diameter. A larger size of orifice was used for firm compounds than for soft ones.

FIGS. 3 and 4 show a series of flow curves (11-15) of gels obtained with five different grades of aromatic extracts supplied by BP Trading under the classification Light IS, 50l LT, 1665, 160/95 and 620/95 respectively (subsequently re-classified as Everflex 81, 553, 84, 65 and 58 respectively). These aromatic extracts, which have less than 40 percent paraffinic carbon, were compounded with a fixed quantity of Baragel 24 (modified clay) and propylene carbonate (polar additive), according to the following composition:

94 parts by weight 6 parts by weight 0.6 parts by weight Aromatic extract Baragcl 24 Propylene carbonate The flow curves are characterised by:

FIG. 3 refers to measurements made at room temperature (22C) with an extrusion orifice diameter of 0.076 inch (2mm). FIG. 4 shows results on the same compounds at C, using a 0.030 inch (0.76 mm) orifice. The smaller orifice for 70C was necessary because of the considerable reduction in viscosity at this temperature, but simple theory of capillary flow of a Bingham material having a specified yield point enables an approximate conversion to be made to a common orifice diameter.

The net conclusion from these curves is that while the true viscosity (proportional to the incremental rate of increase of pressure per unit increase of flow rate) for pressures exceeding P,, is of the same order as that of the base liquids and decreases by 2040 fold from 22C to 70C. the yield stress remains practically constant in agreement with the hypothetical curves of FIG. 1. Furthermore the yield pressure P has the same order of magnitude for all the compounds illustrated in FIGS. 3 and 4, i.e. of the order 23 lb per square inch (psi). The yield strength necessary to prevent drainage of a filling material under its own weight in a vertical cable depends upon the diameter of the interstices between strands, but in a test such as is described above with a 0.076 inch orifice the corresponding value of P,, required is of the order 0.05 psi. A considerable safety margin would be added in practice, but a P value of 0.5 psi can be considered adequate.

The slope of the flow characteristic at which the viscosity becomes excessively high for pumping depends upon the manufacturing set-up used for transferring the filling compound during the stranding operation. However, practical experience in the use of petrolatum as a filler enables a limiting characteristic to be approximately positioned at curve of FIG. 3.

It is of course the value of the apparent viscosity at the actual pumping pressure (proportional to flow rate per unir of pressure) which is the critical parameter concerning suitability for pumping, but since suitable pumping pressures are not the same for all varieties and sizes of cable, and also acceptable flow rates will depend in part upon the geometry of the cable, it is convenient to provide a rough guide of suitability for pumping in terms of a given flow rate etc. at an arbitrary pressure. We have found a suitable guide to the limit of suitability for pumping is the requirement that under an extrusion pressure of 12 psi there should be a flow rate of not less than 1 gm/minute through an orifree 2 mm in diameter and 2 cm long. This guide is based on the assumption that the flow properties of the compound do not depart radically from Bingham flow and that the yield pressure of the compound in an orifice with the above aspect ratio 10:1 lies in the region 0.5 to 3 psi. The minimum flow rate will have to be achieved at a temperature of about 22C if room temperature pumping is desired.

Properties of the above compositions are given by way of example, but are not to be regarded as limiting. The characteristic flow curves may be varied at will by modifying the quantities of gellant and liquid polar additive, separately or simultaneously, relatively to that of the major liquid constituent.

It is to be noted that due to insensitivity of the yield stress of these compositions to temperature, the balland-ring softening point commonly quoted for filling compounds is in all cases above 100C. For comparison, the corresponding softening points of petrolatums at present used cannot be raised much above 65-70C without detriment to pumping characteristics and low temperature flexibility. Another feature of these gels formed with a gellant which is insoluble in the dispersant and does not melt below 100C is a low thermal expansion due to absence of a change of state of gellant during temperature cycling. For example a typical volume change on cooling from 80C to room temperature is approximately 4 percent, which must be compared with a corresponding change of approximately 10 percent for petrolatums. A further feature is that there was no appreciable phase separation when these compounds were stored for an extended period at 80C; oil separation is commonly observed when petrolatums with drop points as high as are stored for equal periods at 50C.

A smaller quantity of gellant was employed in making gels from the following range of relatively high viscosity (-35 centi-stokes at C) oils having a higher paraffinic carbon content:

Catenex 79 (Shell-Mex & BP), Servis (Gulf), Cylrex FM (Mobil), and Sunpar 2280 (British Sun Oil Company). In each case a gel satisfactory for use as a water blocking compound was obtained by blending 96 /2 wt7( of the oil with 3 wt% of Bentone 38 and 0.45 wt% polar additive in the form of propylene carbonate.

The higher paraffinic carbon content of these oils (typically in the region of 70 i 5 percent paraffinic carbon) provides a reduced temperature coefficient of viscosity. Another difference is that the molecular weight of these oils is approximately twice that of the aromatic oils previously referred to, and yet they are not too viscous to be readily blended with gellant at room temperature. These factors militate toward producing with less gellant a water blocking gel that is less liable to degrade at high service temperatures certain cable insulation and cable sheathing materials such as polyolefins. Another advantage is that these oils have a greater volume resistivity than the aromatic oils previously referred to, and they are less toxic. An advantage of the aromatic oils is that they are more readily blended to form gels. Thus while premixing with a medium speed mixer was preferred with the aromatic oils in order to prevent premature jellation, premixing with a high speed mixer is preferred with the paraffinic oils. For instance in blending Catenex 79 it was found possible to follow high speed premixing immediately with colloid milling to produce a satisfactory gel, whereas if the premixing was performed at medium speed no gel was formed. High speed premixing was not essential however since adequate gels were produced if the premix was allowed to stand for a few days before colloid milling, or if the product of immediate colloid milling was allowed to stand for a day and then repassed through the colloid mill.

In order to meet a specification requiring a greater volume resistivity than was provided by the gels consisting of the paraffinic oils blended with Bentone 38 a satisfactory water blocking gel was formed by dispers ing 6 wt% of sub-micron particle sized silica (Aerosil 200) in 94 wt% Catenex 79.

It is to be understood that the foregoing description of specific examples of this invention is made by way of example only and is not to be considered as a limitation on its scope.

We claim:

1. A water blocking composition for sheathed stranded cables consisting essentially of a gel of (a) a major proportion by weight of a substantially nonvolatile petroleum based oil, said oil being an aromatic extract containing aromatic and saturated hydrocarbons and sulfur containing polar compounds, in which has been dispersed (b) a minor proportion by weight of a solid gellant which is insoluble in said oil and which does not melt below 100C, said gellant being selected from the group consisting of a bentonite clay based gellant and a sub-micron particle sized silica gellant, the gel being substantially devoid of any gellant which is soluble in the oil and melts below 100C.

2. A water blocking composition as claimed in claim 1 wherein the gellant is a bentonite clay based gellant.

3. A water blocking composition as claim in claim 1 wherein the gellant is sub-micron particle sized silica. =1 l l 

1. A WATER BLOCKING COMPOSITION FOR SHEATHED STRANDED CABLES CONSISTING ESSENTIALLY OF A GEL OF (A) A MAJOR PROPORTION BY WEIGHT OF A SUBSTANTIALLY NON-VOLATILE PETROLEUM BASED OIL, SAID OIL BEING AN AROMATIC EXTRACT CONTAINING AROMATIC AND SATURATED HYDROCARBONS AND SULFUR CONTAINING POLAR COMPOUNDS, IN WHICH HAS BEEN DISPERSED (B) A MINOR PROPORTION BY WEIGHT OF A SOLID GELLANT WHICH IS INSOLUBLE IN SAID OIL AND WHICH DOES NOT MELT BELOW 100*C, SAID GELLANT BEING SELECTED FROM THE GROUP CONSISTING OF A BENTONITE CLAY BASED GELLANT AND A SUB-MICRON PARTICLE SIZED SILICA GELLANT, THE GEL BEING SUBSTANTIALLY DEVOID OF ANY GELLANT WHICH IS SOLUBLE IN THE OIL AND MELTS BELOW 100*C.
 2. A water blocking composition as claimed in claim 1 wherein the gellant is a bentonite clay based gellant.
 3. A water blocking composition as claim in claim 1 wherein the gellant is sub-micron particle sized silica. 